WO2003067679A1 - Procede permettant de former des dispositifs electroluminescents - Google Patents

Procede permettant de former des dispositifs electroluminescents Download PDF

Info

Publication number
WO2003067679A1
WO2003067679A1 PCT/GB2003/000542 GB0300542W WO03067679A1 WO 2003067679 A1 WO2003067679 A1 WO 2003067679A1 GB 0300542 W GB0300542 W GB 0300542W WO 03067679 A1 WO03067679 A1 WO 03067679A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
rare earth
iii
formula
polymer
Prior art date
Application number
PCT/GB2003/000542
Other languages
English (en)
Inventor
Poopathy Kathirgamanathan
Original Assignee
Elam-T Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elam-T Limited filed Critical Elam-T Limited
Priority to JP2003566917A priority Critical patent/JP2005517271A/ja
Priority to EP03737380A priority patent/EP1472749A1/fr
Priority to AU2003244412A priority patent/AU2003244412A1/en
Priority to US10/503,835 priority patent/US20050084605A1/en
Publication of WO2003067679A1 publication Critical patent/WO2003067679A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/611—Charge transfer complexes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

Definitions

  • the present invention relates to a method of forming electroluminescent devices.
  • Liquid crystal devices and devices which are based on inorganic semiconductor systems are widely used, however these suffer from the disadvantages of high energy consumption, high cost of manufacture, low quantum efficiency and the inability to make flat panel displays.
  • Organic polymers have been proposed as useful in electroluminescent devices, but it is not possible to obtain pure colours, they are expensive to make and have a relatively low efficiency.
  • aluminium quinolate Another compound which has been proposed is aluminium quinolate, but this requires dopants to be used to obtain a range of colours and has a relatively low efficiency.
  • PCT/GB02/02094, PCT/GB02/02092, PCT/GB02/02093, PCT/GB02/02722, PCT/GB02/003163, PCT/GB02/003588, PCT/GB02/004761 describes a range of complexes and structures including those using lanthanides, actinides and other rare earth chelates which can be used in electroluminescent devices which have improved properties and give better results.
  • US Patent 5128587 discloses an electroluminescent device which consists of an organometallic complex of rare earth elements of the lanthanide series sandwiched between a transparent electrode of high work function and a second electrode of low work function with a hole conducting layer interposed between the electroluminescent layer and the transparent high work function electrode and an electron conducting layer interposed between the electroluminescent layer and the electron injecting low work function anode.
  • the hole conducting layer and the electron conducting layer are required to improve the working and the efficiency of the device.
  • the hole transporting layer serves to transport holes and to block the electrons, thus preventing electrons from moving into the electrode without recombining with holes. The recombination of carriers therefore mainly takes place in the emitter layer.
  • an electroluminescent device in which an electroluminescent material is deposited on a substrate by inkjet printing.
  • Ink-jet is a non-impact dot-matrix printing technology in which droplets of ink are jetted from a small aperture directly to a specified position on a media to create an image.
  • Ink-jet printing has been implemented in many different designs and has a wide range of potential applications. Fundamentally, ink-jet printing is divided into the continuous and the drop-on-demand ink-jet methods.
  • Dr. Sweet of Stanford University demonstrated that by applying a pressure wave pattern to an orifice, the ink stream could be broken into droplets of uniform size and spacing.
  • an electric charge could be impressed on the drops selectively and reliably as they formed out of the continuous ink stream.
  • the charged drops when passing through the electric field were deflected into a gutter for recirculation, and those uncharged drops could fly directly onto the media to form an image. 4
  • This printing process is known as a continuous ink-jet.
  • the continuous ink-jet can be designed as a binary or multiple deflection system.
  • the drops are either charged or uncharged.
  • the charged drops are allowed to fly directly onto the media, while the uncharged drops are deflected into a gutter for recirculation
  • drops are charged and deflected to the media at different levels. The uncharged drops fly straight to a gutter to be recirculated.
  • a drop-on-demand device ejects ink droplets only when they are used in imaging on the media. This approach eliminates the complexity of drop charging and deflection hardware as well as the inherent unreliability of the ink recirculation systems required for the continuous ink-jet technology.
  • thermal ink jet printing employs a process of super-heating the ink inside the print cartridge to about 400 degrees. As the ink heats up, vapour bubbles are formed inside the cartridge, which' expand, explode, and then force ultra-fine droplets of ink out of the printhead's micron-size nozzles and onto the media. As the ink leaves the nozzle head, it creates a vacuum that pulls in fresh ink. This process is repeated thousands of times per second.
  • Thermal ink jet printers are described in US Patents 4,463,359 4,463,359 4,275,290 and nozzle configurations are described in US Patents 4,106,976 to 4,157,935.
  • Piezo ink jet printing relies on different principles for the expulsion of ink from the cartridge nozzles.
  • an electrical charge is applied to the cartridge nozzles and excites a small piezo crystal that is inside.
  • the piezoelectric crystals When the piezoelectric crystals are stimulated, the crystals change shape and squeeze the ink chamber. This action is similar to the action of squeezing an oil can, and forcefully expels the ink from the nozzle tip. Since the piezoelectric process does not utilize heat, printheads can use a wider range of inks than thermal inkjet printers because the heat is removed from the process. This means that solvent-based ink systems and pigmented-ink formulations will be more readily available, which increases the development capabilities for better inks in the future.
  • a squeeze-mode ink-jet can be designed with a thin tube of piezoceramic surrounding a glass nozzle or with a piezoceramic tube cast in plastic that encloses the ink channel
  • the piezoceramic plates are bonded to the diaphragm forming an array of bilaminar electromechanical transducers used to eject the ink droplets.
  • a push-mode design as the piezoceramic rods expand, they push against ink to eject the droplets.
  • piezodrivers can directly contact and push against the ink.
  • a thin diaphragm between piezodrivers and ink is incorporated to prevent the undesirable interactions between ink and piezodriver materials.
  • the electric field generated between the electrodes is in parallel with the polarization of the piezomaterial.
  • the electric field is designed to be perpendicular to the polarization of the piezodriver.
  • the shear action deforms the piezoplates against ink to eject the droplets.
  • the piezodriver becomes an active wall in the ink chamber.
  • Interaction between ink and piezomaterial is one of the key parameters of a shear-mode printhead design.
  • Most, if not all, of the drop-on-demand ink-jet printers on the market today are using either the thermal or piezoelectric principle. Both the electrostatic ink-jet and acoustic ink-jet methods are still in the development stage with many patents pending and few commercial products available.
  • solid ink or hot melt or phase-change ink
  • phase-change ink is solid at room temperature.
  • the ink is jetting as molten liquid drops.
  • Phase-change ink is also called hot melt or solid ink.
  • the ink is jetted out from the printhead as a molten liquid. Upon hitting a recording surface, the molten ink drop solidifies immediately, thus preventing the ink from spreading or penetrating the printed media
  • a typical electroluminescent device will comprise (i) a first electrode, (ii) a hole transporting layer (iii) a layer consisting of an electroluminescent material, (iv) an electron transporting layer and (v) a second electrode.
  • Each of the layers can be deposited by inkjet printing or only the electroluminescent layer.
  • any of the known ink jet printing methods e.g. as referred to above can be used.
  • the continuous and the drop-on-demand ink-jet methods and Piezo ink jet printing can be used if the material to be deposited is in the form of a solution in a solvent.
  • the solvent which is used will depend on the material but chlorinated hydrocarbons such as dichloromethane, n-methyl pyrrolidone, dimethyl sulphoxide, tetrahydrofuran dimetliylformamide etc. are suitable in many
  • solid ink or hot melt or phase-change ink
  • the material which is solid at room temperature is jetted as molten liquid drops on to the substrate
  • the ink jet printing can be used to deposit controlled amounts of the material to be deposited and can be controlled to deposit the material in the precise location.
  • a mixture of the materials is placed in the cartridge of the ink jet printer.
  • the deposition can take place in a vacuum or other atmosphere if desired.
  • the electroluminescent compounds which can be used as the electroluminescent materials in the present invention are of general formula (L ⁇ ) n M where M is a rare earth, lanthanide or an actinide, L ⁇ is an organic complex and n is the valence state of M.
  • Preferred electroluminescent compounds which can be used in the present invention are of formula
  • L ⁇ and Lp are organic ligands
  • M is a rare earth, transition metal, lanthanide or an actinide and n is the valence state of the metal M.
  • the ligands L ⁇ can be the same or different and there can be a plurality of ligands Lp which can be the same or different.
  • L (L )(L 3 )(L..)M (Lp) where M is a rare earth, transition metal, lanthanide or an actinide and (L ⁇ XL 2 )(L 3 )(L...) are the same or different organic complexes and (Lp) is a neutral ligand.
  • the total charge of the ligands (L])(L 2 )(L 3 )(L..) is equal to the valence state of the metal M.
  • the complex has the formula (L ⁇ )(L )(L 3 )M (Lp) and the different groups (L ⁇ )(L 2 )(L 3 ) may be the same or different Lp can be monodentate, bidentate or polydentate and there can be one or more ligands Lp.
  • M is metal ion having an unfilled inner shell and the preferred metals are selected from Sm(III), Eu(II), Eu(III), Tb(III), Dy(III), Yb(IH), Lu(III), Gd (III), Gd(ffl) U(III), Tm(III), Ce (III), Pr( ⁇ i), Nd(III), Pm(i ⁇ ), Dy(Ifl), Ho(III), Er(i ⁇ ) and more preferably Eu(III), Tb(III), Dy( ⁇ i), Gd (III).
  • electroluminescent compounds which can be used in the present invention are of general formula (L ⁇ ) ⁇ M ⁇ M 2 where Mi is the same as M above, M 2 is a non rare earth metal, L ⁇ is a as above and n is the combined valence state of Mi and M .
  • the complex can also comprise one or more neutral ligands Lp so the complex has the general formula (L ⁇ ) n Mi M 2 (Lp), where Lp is as above.
  • the metal M 2 can be any metal which is not a rare earth, transition metal, lanthanide or an actinide examples of metals which can be used include lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (II), lead (IV) and metals of the first, second and third groups of transition metals in different valence states e.g.
  • organometallic complexes which can be used in the present invention are binuclear, trinuclear and polynuclear organometallic complexes e.g. of formula
  • L is a bridging ligand and where Mi is a rare earth metal and M 2 is Mi or a non rare earth metal, Lm and Lu are the same or different organic ligands L ⁇ as defined above, x is the valence state of Mi and y is the valence state of M 2 .
  • trinuclear there are three rare earth metals joined by a metal to metal bond i.e. of formula
  • Ln and Lp are organic ligands L ⁇ and x is the valence state of M-i, y is the valence state of M 2 and z is the valence state of M 3 .
  • Lp can be the same as Lm and Ln or different.
  • the rare earth metals and the non rare earth metals can be joined together by a metal to metal bond and/or via an intermediate bridging atom, ligand or molecular group.
  • the metals can be linked by bridging ligands e.g.
  • polynuclear there are more than three metals joined by metal to metal bonds and/or via intermediate ligands
  • M 1 M 2 M 4 M 3 where Mi, M 2 , M 3 and i are rare earth metals and L is a bridging ligand.
  • the metal M 2 can be any metal which is not a rare earth, transition metal, lanthanide or an actinide examples of metals which can be used include lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper, silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin, antimony, lead, and metals of the first, second and third groups of transition metals e.g.
  • L ⁇ is selected from ⁇ diketones such as those of formulae
  • Ri , R 2 and R 3 can be the same or different and are selected from hydrogen, and substituted and unsubstituted hydrocarbyl groups such as substituted and unsubstituted aliphatic groups, substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups; R ⁇ ; R 2 and R 3 can also form substituted and unsubstituted fused aromatic, heterocyclic and polycyclic ring structures and can be copolymerisable with a monomer e.g. styrene.
  • X is Se, S or O,
  • Y can be hydrogen, substituted or unsubstituted hydrocarbyl groups, such as substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorine, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups or nitrile.
  • Examples of Ri and/or R and/or R 3 include aliphatic, aromatic and heterocyclic alkoxy, aryloxy and carboxy groups, substituted and substituted phenyl, fluorophenyl, biphenyl, phenanthrene, anthracene, naphthyl and fluorene groups alkyl groups such as t-butyl, heterocyclic groups such as carbazole.
  • Some of the different groups L may also be the same or different charged groups such as carboxylate groups so that the group Li can be as defined above and the groups L 2 , L 3 ... can be charged groups such as
  • Ri R 2 and R 3 can also be
  • X is O, S, Se or NH.
  • a preferred moiety Ri is trifluoromethyl CF 3 and examples of such diketones are, banzoyltrifluoroacetone, p-chlorobenzoyltrifluoroacetone, p-bromotrifluoroacetone, p-phenyltrifluoroacetone, 1 -naphthoyltrifluoroacetone, 2-naphthoyltrifluoroacetone, 2-phenathoyltrifluoroacetone, 3-phenanthoyltrifluoroacetone, 9- anthroyltrifluoroacetonetrifluoroacetone, cinnamoyltrifluoroacetone, and 2- thenoyltrifluoroacetone.
  • the different groups L may be the same or different ligands of formulae
  • the different groups L may be the same or different quinolate derivatives such as
  • the different groups L may also be the same or different carboxylate groups e.g.
  • R 5 is a substitated or unsubstituted aromatic, polycyclic or heterocyclic ring a polypyridyl group
  • R 5 can also be a 2-ethyl hexyl group so L n is 2-ethylhexanoate or R 5 can be a chair structure so that L n is 2-acetyl cyclohexanoate or L ⁇ can be
  • R is as above e.g. alkyl, allenyl, amino or a fused ring such as a cyclic or polycyclic ring.
  • the different groups L may also be
  • the groups Lp can be selected from
  • each Ph which can be the same or different and can be a phenyl (OP ⁇ P) or a substituted phenyl group, other substitated or unsubstitated aromatic group, a substituted or unsubstituted heterocyclic or polycyclic group, a substitated or unsubstituted fused aromatic group such as a naphthyl, anthracene, phenanthrene or pyrene group.
  • the substituents can be for example an alkyl, aralkyl, alkoxy, aromatic, heterocyclic, polycyclic group, halogen such as fluorine, cyano, amino. Substitated amino etc. Examples are given in figs.
  • R, R 1; R 2; R 3 and i can be the same or different and are selected from hydrogen, hydrocarbyl groups, substitated and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups;
  • R, Ri, R 2) R 3 and i can also form substituted and unsubstituted fused aromatic, heterocyclic and polycyclic ring structures and can be copolymerisable with a monomer e.g. styrene.
  • R, R lt R 2; R 3 and Ri can also be ' unsaturated alkylene groups such as vinyl groups or groups
  • L p can also be compounds of formulae
  • L p can also be
  • L p chelates are as shown in figs. 4 and fluorene and fluorene derivatives e.g. a shown in figs. 5 and compounds of formulae as shown as shown in figs. 6 to 8.
  • L ⁇ and Lp are tripyridyl and TMHD, and TMHD complexes, ⁇ , ⁇ ', ⁇ " tripyridyl, crown ethers, cyclans, cryptans phthalocyanans, porphoryins ethylene diamine tetramine (EDTA), DCTA, DTPA and TTHA.
  • TMHD 2,2,6,6-tetramethyl-3,5-heptanedionato
  • OPNP is diphenylphosphonimide triphenyl phosphorane.
  • the formulae of the polyamines are shown in fig. 11.
  • electroluminescent materials which can be used include metal quinolates such as lithium quinolate, and non rare earth metal complexes such as aluminium, magnesium, zinc and scandium complexes such as complexes of ⁇ -diketones e.g. Tris -(l,3-diphenyl-l-3-propanedione) (DBM) and suitable metal complexes are A1(DBM) 3, Zn(DBM) 2 and Mg(DBM) 2. , Sc(DBM) 3 etc.
  • metal quinolates such as lithium quinolate
  • non rare earth metal complexes such as aluminium, magnesium, zinc
  • scandium complexes such as complexes of ⁇ -diketones e.g. Tris -(l,3-diphenyl-l-3-propanedione) (DBM)
  • suitable metal complexes are A1(DBM) 3, Zn(DBM) 2 and Mg(DBM) 2. , Sc(DBM) 3 etc.
  • the first electrode is preferably a transparent substrate such as is a conductive glass or plastic material which acts as the anode
  • preferred substrates are conductive glasses such as indium tin oxide coated glass, but any glass which is conductive or has a conductive layer such as a metal or conductive polymer can be used.
  • Conductive polymers and conductive polymer coated glass or plastics materials can also be used as the substrate.
  • the hole transporting material can be an amine complex such as poly (vinylcarbazole), N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1' -biphenyl -4,4'- diamine (TPD), an unsubstitated or substitated polymer of an amino substitated aromatic compound, a polyaniline, substitated polyanilines, polythiophenes, substitated polythiophenes, polysilanes etc.
  • polyanilines are polymers of
  • R is in the ortho - or meta-position and is hydrogen, Cl-18 alkyl, Cl-6 alkoxy, amino, chloro, bromo, hydroxy or the group
  • R is alky or aryl and R' is hydrogen, Cl-6 alkyl or aryl with at least one other monomer of formula I above.
  • the hole transporting material can be a polyaniline
  • polyanilines which can be used in the present invention have the general formula
  • XXVII where p is from 1 to 10 and n is from 1 to 20, R is as defined above and X is an anion, preferably selected from CI, Br, SO 4 , BF 4 , PF 6 , H 2 PO 3 , H 2 PO 4 , arylsulphonate, arenedicarboxylate, polystyrenesulphonate, polyacrylate alkysulphonate, vinylsulphonate, vinylbenzene sulphonate, cellulose sulphonate, camphor sulphonates, cellulose sulphate or a perfluorinated polyanion.
  • arylsulphonates are p-toluenesulphonate, benzenesulphonate, 9,10- anthraquinone-sulphonate and anthracenesulphonate, an example of an arenedicarboxylate is phthalate and an example of arenecarboxylate is benzoate.
  • evaporable deprotonated polymers of unsubstituted or substituted polymer of an amino substitated aromatic compound are used.
  • the de-protonated unsubstituted or substitated polymer of an amino substituted aromatic compound can be formed by deprotonating the polymer by treatment with an alkali such as ammonium hydroxide or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • the degree of protonation can be controlled by forming a protonated polyaniline and de-protonating.
  • Methods of preparing polyanilines are described in the article by A. G. MacDiarmid and A. F. Epstein, Faraday Discussions, Chem Soc.88 P319 1989.
  • the conductivity of the polyaniline is dependant on the degree of protonation with the maximum conductivity being when the degree of protonation is between 40 and 60% e.g. about 50% for example.
  • a polyaniline can be formed of octamer units i.e. p is four e.g.
  • the polyanilines can have conductivities of the order of 1 x 10 "1 Siemen cm "1 or higher.
  • the aromatic rings can be unsubstitated or substitated e.g. by a CI to 20 alkyl group such as ethyl.
  • the polyaniline can be a copolymer of aniline and preferred copolymers are the copolymers of aniline with o-anisidine, m-sulphanilic acid or o-aminophenol, or o- toluidine with o-aminophenol, o-ethylaniline, o-phenylene diamine or with amino anthracenes.
  • polymers of an amino substituted aromatic compound which can be used include substitated or unsubstituted polyaminonapthalenes, polyaminoanthracenes, polyaminophenanthrenes, etc. and polymers of any other condensed polyaromatic compound.
  • Polyaminoanthracenes and methods of making them are disclosed in US Patent 6,153,726.
  • the aromatic rings can be unsubstituted or substituted e.g. by a group R as defined above.
  • conjugated polymer and the conjugated polymers which can be used can be any of the conjugated polymers disclosed or referred to in US 5807627, PCT/WO90/13148 and PCT/WO92/03490.
  • the preferred conjugated polymers are poly (p-phenylenevinylene)-PPV and copolymers including PPV.
  • Other preferred polymers are poly(2,5 dialkoxyphenylene vinylene) such as poly (2-methoxy-5-(2-methoxypentyloxy-l,4-phenylene vinylene), poly(2-methoxypentyloxy)- 1 ,4-phenylenevinylene), poly(2-methoxy-5-(2- dodecyloxy-l,4-phenylenevinylene) and other poly(2,5 dialkoxyphenylenevinylenes) with at least one of the alkoxy groups being a long chain solubihsing alkoxy group, poly fluorenes and oligofluorenes, polyphenylenes and oligophenylenes, polyanthracenes and oligo anthracenes, ploythiophenes and oligothiophenes.
  • the phenylene ring may optionally carry one or more substitaents e.g. each independently selected from alkyl, preferably methyl, alkoxy, preferably methoxy or ethoxy.
  • Any poly(arylenevinylene) including substituted derivatives thereof can be used and the phenylene ring in poly(p-phenylenevinylene) may be replaced by a fused ring system such as anthracene or naphthlyene ring and the number of vinylene groups in each polyphenylenevinylene moiety can be increased e.g. up to 7 or higher.
  • the conjugated polymers can be made by the methods disclosed in US 5807627, PCT/WO90/13148 and PCT/WO92/03490.
  • the thickness of the hole transporting layer is preferably 20nm to 200nm.
  • polymers of an amino substitated aromatic compound such as polyanilines referred to above can also be used as buffer layers with or in conjunction with other hole transporting materials.
  • Ri , R 2 and R 3 can be the same or different and are selected from hydrogen, and substitated and unsubstituted hydrocarbyl groups such as substituted and unsubstitated aliphatic groups, substitated and unsubstitated aromatic, heterocyclic and polycyclic ring structures, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups; Ri, R 2 and R 3 can also form substitated and unsubstitated fused aromatic, heterocyclic and polycyclic ring structures and can be copolymerisable with a monomer e.g.
  • styrene X is Se, S or O
  • Y can be hydrogen, substitated or unsubstituted hydrocarbyl groups, such as substituted and unsubstitated aromatic, heterocyclic and polycyclic ring structures, fluorine, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups or nitrile.
  • Ri and/or R 2 and/or R 3 examples include aliphatic, aromatic and heterocyclic alkoxy, aryloxy and carboxy groups, substitated and substituted phenyl, fluorophenyl, biphenyl, phenanthrene, anthracene, naphthyl and fluorene groups alkyl groups such as t-butyl, heterocyclic groups such as carbazole.
  • the electron injecting material is a material which will transport electrons when an electric current is passed through electron injecting materials include a metal complex such as a metal quinolate e.g. an aluminium quinolate, lithium quinolate, a cyano anthracene such as 9,10 dicyano anthracene, cyano substitated aromatic compounds, tetracyanoquinidodimethane a polystyrene sulphonate or a compound with the structural formulae shown in figures 9 and 10 of the drawings in which the phenyl rings can be substituted with substitaents R as defined above.
  • the electron injecting material can be mixed with the electroluminescent material and co- deposited with it.
  • the second electrode functions as the cathode and can be any low work function metal e.g. aluminium, calcium, lithium, silver/magnesium alloys, rare earth metal alloys etc., aluminium is a preferred metal.
  • a metal fluoride such as an alkali metal, rare earth metal or their alloys can be used as the second electrode for example by having a metal fluoride layer formed on a metal.
  • the hole transporting material can be mixed with the electroluminescent material and co-deposited with it.
  • the hole transporting materials, the electroluminescent material and the electron injecting materials can be mixed together to form one layer, which simplifies the construction.
  • the display of the invention may be monochromatic or polychromatic. Electroluminescent rare earth chelate compounds are known which will emit a range of colours e.g. red, green, and blue light and white light and examples are disclosed in Patent Applications WO98/58037 PCT/GB98/01773, PCT/GB99/03619, PCT/GB99/04030, PCT/GB99/04024, PCT/GB99/04028, PCT/GB00/00268 and can be used to form OLEDs emitting those colours.
  • a full colour display can be formed by arranging three individual backplanes, each emitting a different primary monochrome colour, on different sides of an optical system, from another side of which a combined colour image can be viewed.
  • rare earth chelate electroluminescent compounds emitting different colours can be fabricated so that adjacent diode pixels in groups of three neighbouring pixels produce red, green and blue light.
  • field sequential colour filters can be fitted to a white light emitting display.
  • Electrodes can be formed of silicon and the electroluminescent material and intervening layers of a hole transporting and electron transporting materials can be formed as pixels on the silicon substrate.
  • each pixel comprises at least one layer of a rare earth chelate electroluminescent material and an (at least semi-) transparent electrode in contact with the organic layer on a side thereof remote from the substrate.
  • the substrate is of crystalline silicon and the surface of the substrate may be polished or smoothed to produce a flat surface prior to the deposition of electrode, or electroluminescent compound.
  • a non-planarised silicon substrate can be coated with a layer of conducting polymer to provide a smooth, flat surface prior to deposition of further materials.
  • each pixel comprises a metal electrode in contact with the substrate.
  • metal electrode in contact with the substrate.
  • either may serve as the anode with the other constituting the cathode.
  • an indium tin oxide coated glass can act as the anode and light is emitted through the anode.
  • the cathode can be formed of a transparent electrode which has a suitable work function, for example by a indium zinc oxide coated glass in which the indium zinc oxide has a low work function.
  • the anode can have a transparent coating of a metal formed on it to give a suitable work function.
  • the metal electrode may consist of a plurality of metal layers, for example a higher work function metal such as aluminium deposited on the substrate and a lower work function metal such as calcium deposited on the higher work function metal.
  • a further layer of conducting polymer lies on top of a stable metal such as aluminium.
  • the electrode also acts as a mirror behind each pixel and is either deposited on, or sunk into, the planarised surface of the substrate.
  • the electrode may alternatively be a light absorbing black layer adjacent to the substrate.
  • selective regions of a bottom conducting polymer layer are made non-conducting by exposure to a suitable aqueous solution allowing formation of arrays of conducting pixel pads which serve as the bottom contacts of the pixel electrodes.
  • the brightness of light emitted from each pixel is preferably controllable in an analogue manner by adjusting the voltage or current applied by the matrix circuitry or by inputting a digital signal which is converted to an analogue signal in each pixel circuit.
  • the substrate preferably also provides data drivers, data converters and scan drivers for processing information to address the array of pixels so as to create images.
  • an electroluminescent material which emits light of a different colour depending on the applied voltage the colour of each pixel can be controlled by the matrix circuitry.
  • each pixel is controlled by a switch comprising a voltage controlled element and a variable resistance element, both of which are conveniently formed by metal-oxide-semiconductor field effect transistors (MOSFETs) or by an active matrix transistor.
  • MOSFETs metal-oxide-semiconductor field effect transistors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un procédé permettant de former un dispositif électroluminescent. Selon ce procédé, le matériau électroluminescent est déposé par impression par jet d'encre.
PCT/GB2003/000542 2002-02-08 2003-02-06 Procede permettant de former des dispositifs electroluminescents WO2003067679A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2003566917A JP2005517271A (ja) 2002-02-08 2003-02-06 エレクトロルミネセンス素子の製造方法
EP03737380A EP1472749A1 (fr) 2002-02-08 2003-02-06 Procede permettant de former des dispositifs electroluminescents
AU2003244412A AU2003244412A1 (en) 2002-02-08 2003-02-06 Method for forming electroluminescent devices
US10/503,835 US20050084605A1 (en) 2002-02-08 2003-02-06 Method for forming electroluminescent devices

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0202997.3 2002-02-08
GBGB0202997.3A GB0202997D0 (en) 2002-02-08 2002-02-08 Method for forming electroluminescent devices

Publications (1)

Publication Number Publication Date
WO2003067679A1 true WO2003067679A1 (fr) 2003-08-14

Family

ID=9930705

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/000542 WO2003067679A1 (fr) 2002-02-08 2003-02-06 Procede permettant de former des dispositifs electroluminescents

Country Status (7)

Country Link
US (1) US20050084605A1 (fr)
EP (1) EP1472749A1 (fr)
JP (1) JP2005517271A (fr)
AU (1) AU2003244412A1 (fr)
GB (1) GB0202997D0 (fr)
TW (1) TW200303697A (fr)
WO (1) WO2003067679A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1862497A2 (fr) * 2000-06-12 2007-12-05 Sumation Co., Ltd. Matériaux et dispositifs électroluminescents à matrice de polymère
JP2008004950A (ja) * 2007-07-27 2008-01-10 Semiconductor Energy Lab Co Ltd 電界発光素子用材料、及びそれを用いた電界発光素子
JP2008519427A (ja) * 2004-11-03 2008-06-05 オーエルイーディー−ティー リミテッド 緩衝層
CN100413116C (zh) * 2003-01-23 2008-08-20 精工爱普生株式会社 有机电致发光装置的制造方法、及其电子装置
US8883325B2 (en) 2006-12-29 2014-11-11 Merck Patent Gmbh Electroluminescent device using azomethine-lithium-complex as electron injection layer
CN104804028A (zh) * 2015-05-07 2015-07-29 哈尔滨工业大学 一种手性的蓝光材料3d铟-钾异金属有机框架及其模板合成方法和应用
RU2657496C1 (ru) * 2017-07-10 2018-06-14 Сиа Эволед Разнолигандные фторзамещенные ароматические карбоксилаты лантанидов, проявляющие люминесцентные свойства, и органические светодиоды на их основе
WO2019031809A3 (fr) * 2017-08-08 2019-04-25 Rohm And Haas Electronic Materials Korea Ltd. Matériau à changement de phase utilisé dans la production de diodes électroluminescentes organiques

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8214185B2 (en) * 2005-05-13 2012-07-03 Seiko Epson Corporation Stability performance of the coupled algorithms for viscoelastic ink jet simulations
US7478023B2 (en) * 2005-05-13 2009-01-13 Seiko Epson Corporation Coupled algorithms for viscoelastic ink-jet simulations
US7921001B2 (en) * 2005-08-17 2011-04-05 Seiko Epson Corporation Coupled algorithms on quadrilateral grids for generalized axi-symmetric viscoelastic fluid flows
US7828424B2 (en) * 2006-05-19 2010-11-09 Xerox Corporation Heater and drip plate for ink loader melt assembly
DE102006048202A1 (de) * 2006-10-11 2008-04-17 Universität Regensburg Lanthanoid-Emitter für OLED-Anwendungen
KR101484453B1 (ko) * 2011-10-25 2015-01-19 다이니폰 인사츠 가부시키가이샤 정공 주입 수송층용 재료, 정공 주입 수송층 형성용 잉크, 디바이스 및 이들의 제조 방법
JP6425395B2 (ja) * 2014-03-14 2018-11-21 出光興産株式会社 インク組成物、インク組成物を用いた有機エレクトロルミネッセンス素子、及び電子機器
JP2015120914A (ja) * 2014-12-24 2015-07-02 学校法人北里研究所 フッ素置換ジベンゾイルメタニドを配位子とするアルミニウム錯体を含む発光材料及び有機ｅｌ素子

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932139A (en) * 1994-03-17 1999-08-03 Hitachi Maxell, Ltd. Fluorescent substance, fluorescent composition, fluorescent mark carrier and optical reader thereof
WO1999043031A1 (fr) * 1998-02-23 1999-08-26 Cambridge Display Technology Ltd. Dispositifs d'affichage
WO2000032719A1 (fr) * 1998-12-02 2000-06-08 South Bank University Enterprises Ltd. Procede de formation de films ou de couches
JP2000160083A (ja) * 1998-11-24 2000-06-13 Dainippon Toryo Co Ltd ジェット印刷用インク組成物
WO2000044851A2 (fr) * 1999-02-01 2000-08-03 South Bank University Enterprises Ltd Materiaux electroluminescents
EP1083775A1 (fr) * 1999-03-29 2001-03-14 Seiko Epson Corporation Composition, procede de preparation d'un film, et element fonctionnel et son procede de preparation
WO2001041229A1 (fr) * 1999-11-29 2001-06-07 Koninklijke Philips Electronics N.V. Dispositif organique electroluminescent et son procede de fabrication

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989737A (en) * 1997-02-27 1999-11-23 Xerox Corporation Organic electroluminescent devices
US6497969B2 (en) * 1997-09-05 2002-12-24 Nessdisplay Co., Ltd. Electroluminescent device having an organic layer including polyimide
US6252253B1 (en) * 1998-06-10 2001-06-26 Agere Systems Optoelectronics Guardian Corp. Patterned light emitting diode devices
EP1122793A2 (fr) * 2000-02-01 2001-08-08 Canon Kabushiki Kaisha Production d'un dispositif organique luminescent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932139A (en) * 1994-03-17 1999-08-03 Hitachi Maxell, Ltd. Fluorescent substance, fluorescent composition, fluorescent mark carrier and optical reader thereof
WO1999043031A1 (fr) * 1998-02-23 1999-08-26 Cambridge Display Technology Ltd. Dispositifs d'affichage
JP2000160083A (ja) * 1998-11-24 2000-06-13 Dainippon Toryo Co Ltd ジェット印刷用インク組成物
WO2000032719A1 (fr) * 1998-12-02 2000-06-08 South Bank University Enterprises Ltd. Procede de formation de films ou de couches
WO2000044851A2 (fr) * 1999-02-01 2000-08-03 South Bank University Enterprises Ltd Materiaux electroluminescents
EP1083775A1 (fr) * 1999-03-29 2001-03-14 Seiko Epson Corporation Composition, procede de preparation d'un film, et element fonctionnel et son procede de preparation
WO2001041229A1 (fr) * 1999-11-29 2001-06-07 Koninklijke Philips Electronics N.V. Dispositif organique electroluminescent et son procede de fabrication

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1862497A2 (fr) * 2000-06-12 2007-12-05 Sumation Co., Ltd. Matériaux et dispositifs électroluminescents à matrice de polymère
EP1862497A3 (fr) * 2000-06-12 2007-12-12 Sumation Co., Ltd. Matériaux et dispositifs électroluminescents à matrice de polymère
CN100413116C (zh) * 2003-01-23 2008-08-20 精工爱普生株式会社 有机电致发光装置的制造方法、及其电子装置
JP2008519427A (ja) * 2004-11-03 2008-06-05 オーエルイーディー−ティー リミテッド 緩衝層
US8883325B2 (en) 2006-12-29 2014-11-11 Merck Patent Gmbh Electroluminescent device using azomethine-lithium-complex as electron injection layer
US9437828B2 (en) 2006-12-29 2016-09-06 Merck Patent Gmbh Electroluminescent device using azomethine-lithium-complex as electron injection layer
JP2008004950A (ja) * 2007-07-27 2008-01-10 Semiconductor Energy Lab Co Ltd 電界発光素子用材料、及びそれを用いた電界発光素子
CN104804028A (zh) * 2015-05-07 2015-07-29 哈尔滨工业大学 一种手性的蓝光材料3d铟-钾异金属有机框架及其模板合成方法和应用
RU2657496C1 (ru) * 2017-07-10 2018-06-14 Сиа Эволед Разнолигандные фторзамещенные ароматические карбоксилаты лантанидов, проявляющие люминесцентные свойства, и органические светодиоды на их основе
WO2019031809A3 (fr) * 2017-08-08 2019-04-25 Rohm And Haas Electronic Materials Korea Ltd. Matériau à changement de phase utilisé dans la production de diodes électroluminescentes organiques

Also Published As

Publication number Publication date
JP2005517271A (ja) 2005-06-09
GB0202997D0 (en) 2002-03-27
US20050084605A1 (en) 2005-04-21
TW200303697A (en) 2003-09-01
EP1472749A1 (fr) 2004-11-03
AU2003244412A1 (en) 2003-09-02

Similar Documents

Publication Publication Date Title
US20050084605A1 (en) Method for forming electroluminescent devices
TW533446B (en) Electroluminescent device and a method of manufacturing thereof
EP1850368B2 (fr) Composition filmogène et dispositif électroluminescent organique
TWI381566B (zh) 其中一層含有客體材料之電子裝置及形成該電子裝置之方法
US8618561B2 (en) Methods for depositing nanomaterial, methods for fabricating a device, and methods for fabricating an array of devices
US9096425B2 (en) Methods for depositing nanomaterial, methods for fabricating a device, methods for fabricating an array of devices and compositions
CN1879237B (zh) 具有包含客体材料的区域的有机层的形成方法及结合了该层的有机电子器件
JP5259139B2 (ja) 有機電界発光素子用組成物、有機電界発光素子および有機電界発光素子の製造方法
EP1122793A2 (fr) Production d'un dispositif organique luminescent
US20110223340A1 (en) Electro-form nozzle apparatus and method for solution coating
KR101690806B1 (ko) 유기 전계 발광 소자용 잉크젯 잉크 및 유기 전계 발광 소자의 제조 방법
CN102460759A (zh) 用于有机层的喷墨印刷或其他用途的液体组合物
WO2003003794A1 (fr) Element electroluminescent
US20030215669A1 (en) Electroluminescent device
JP2019081868A (ja) インクジェットインキ、およびそれを用いた印刷物、電界発光素子
US20040110866A1 (en) Compressed fluid formulation containing hole transporting material
KR20110107353A (ko) 용액 코팅을 위한 전기-주조 노즐 장치 및 방법
JP2004133050A (ja) 機能性素子基板の製造方法および機能性素子基板および機能性素子基板の使用方法および画像表示装置
US6927415B2 (en) Compressed fluid formulation containing electron transporting material
US8691667B1 (en) Method and apparatus for depositing a pattern on a substrate
JP5580335B2 (ja) 連続印刷用の飛散防止装置および方法
KR20200048819A (ko) 잉크젯 프린팅용 잉크 조성물 및 이를 이용한 패턴 형성방법
JP2003036970A (ja) 電界発光素子の製造方法及び溶液滴下装置

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2003566917

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 10503835

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2003737380

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2003737380

Country of ref document: EP